JP2005128300A - Photosensitive resin composition, photosensitive element using the same, method for making resist pattern, and method for manufacturing printed wiring board and display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in following property and storage stability, a photosensitive element, a method for making a resist pattern, and methods for manufacturing a printed wiring board and a display panel. <P>SOLUTION: The photosensitive resin composition contains a plasticizer having a melting point in the range of 20-130°C, or the photosensitive resin composition contains a plasticizer having a lower melting point than a laminating temperature. The photosensitive resin composition contains (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond per molecule, (C) a photopolymerization initiator and (D) the above plasticizer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for producing a resist pattern, a printed wiring board, and a method for producing a display board.

Conventionally, in the field of printed wiring board production, photosensitive elements obtained using a photosensitive resin composition and a support and a protective film are widely used as resist materials used for etching, plating, and the like. The printed wiring board is formed by laminating a photosensitive element on a copper substrate, pattern exposure, removing an unexposed portion with a developer, performing etching or plating treatment, forming a pattern, It is manufactured by a method in which the cured portion is peeled off from the substrate. On the other hand, the display plate is laminated with a photosensitive element on a base material coated with a rib material, exposed to a pattern, then the unexposed area is removed with a developing solution, subjected to sand blasting to form a pattern, and then a resist. It is manufactured by a method in which a cured portion of the material is peeled off from the substrate.
As a developing solution for removing the unexposed portion, an alkali developing type using a sodium hydrogen carbonate solution or the like has become mainstream, and the developing solution usually has an ability to dissolve the photosensitive resin composition layer to some extent. Any photosensitive resin composition can be dissolved or dispersed in the developer during development.
In recent years, the demand for production of printed wiring boards and display boards at high yields has increased, and the ability to follow the surface of the substrate (the photosensitive resin composition layer is also present in the surface irregularities of the substrate to be laminated) Research has been made on a photosensitive element and a laminating method which are excellent in the property that the material is sufficiently embedded. As a photosensitive element, a method for softening a photosensitive resin composition of a photosensitive element in JP-A-8-95241, JP-A-9-244230, JP-A 2000-10278, and JP-A 2000-181061 However, specific materials are used for the binder polymer and the photopolymerizable compound, and the properties required for some applications cannot be sufficiently obtained, and the versatility is lacking. On the other hand, as for the research on the lamination method, resin is used in JP-A-52-154363, water is used in JP-A-57-21890 and JP-A-57-21891, and JP-A-51-63702. JP-A-53-31670 discloses a method using a vacuum laminator, but the apparatus is expensive and lacks versatility.

JP-A-8-95241 JP-A-9-244230 JP 2000-10278 A JP 2000-181061 A JP-A-52-154363 JP 57-21890 A JP-A-57-21891 Japanese Patent Laid-Open No. 51-63702 JP-A-53-31670

  The present invention is a photosensitive resin composition excellent in followability to the substrate surface while maintaining the characteristics of the conventional photosensitive resin composition, and excellent in storage stability, and a photosensitive element and resist using the same. It aims at providing the manufacturing method of a pattern, the printed wiring board, and the manufacturing method of a display board.

The invention described in claim 1 relates to a photosensitive resin composition comprising a plasticizer having a melting point in the range of 20 to 130 ° C.
The invention described in claim 2 relates to a photosensitive resin composition comprising a plasticizer having a melting point lower than the laminating temperature.
The invention according to claim 3 is the photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule, and (C) light. It relates to the photosensitive resin composition according to claim 1 or 2, comprising a polymerization initiator and (D) a plasticizer.
In the invention according to claim 4, the blending amount of the component (A), the component (B), the component (C) and the component (D) of claim 3 is 100 weights in total of the component (A) and the component (B). Component (A) is 30 to 80 parts by weight, component (B) is 20 to 60 parts by weight, component (C) is 0.1 to 20 parts by weight, and component (D) is 0.1 to 40 parts by weight. It is related with the photosensitive resin composition of Claim 3 formed by mix | blending a part.
The invention according to claim 5 relates to a photosensitive element formed by applying and drying a layer of the photosensitive resin composition according to any one of claims 1 to 4 on a support.
The invention according to claim 6 is a method in which the layer of the photosensitive resin composition according to any one of claims 1 to 4 is applied and dried on a support, and further the photosensitive resin composition on the side opposite to the support. The present invention relates to a photosensitive element formed by laminating a protective film so as to be in contact with an object layer.

The invention according to claim 7 is the photosensitive resin composition according to claim 5 or claim 6, wherein the protective film is peeled off from the photosensitive element, and the photosensitive resin composition is formed on the circuit forming substrate or the display forming substrate. The present invention relates to a method for producing a resist pattern, characterized by laminating layers of objects so as to adhere to each other, irradiating actinic rays in the form of an image, photocuring an exposed portion, and removing an unexposed portion by development.
The invention according to claim 8 relates to a method for manufacturing a printed wiring board, wherein the circuit forming substrate on which the resist pattern is formed is etched or plated by the method for manufacturing a resist pattern according to claim 7. .
A ninth aspect of the present invention relates to a method for manufacturing a display board, comprising the step of processing a display forming substrate on which a resist pattern is formed by sandblasting by the method for manufacturing a resist pattern according to the seventh aspect.

  The photosensitive resin composition of the present invention contains a plasticizer having a melting point in the range of 20 to 130 ° C., or contains a plasticizer having a melting point lower than the laminating temperature. The photosensitive resin composition is excellent in followability to the substrate surface and storage stability while maintaining the above characteristics. A photosensitive element, a resist pattern manufacturing method, a printed wiring board, and a display board manufacturing method using the photosensitive resin composition are excellent in followability to the substrate surface and storage stability. Wiring boards and display boards can be manufactured with high yield.

Hereinafter, the present invention will be described in detail.
The photosensitive resin composition of the present invention comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule, (C) a photopolymerization initiator, and (D ) It is preferable to contain a plasticizer, and (D) the plasticizer needs to have a melting point in the range of 20 to 130 ° C. Further, (D) the plasticizer needs to have a melting point lower than the laminating temperature.

The (D) plasticizer used in the present invention is a substance that does not substantially change the photosensitive properties (photosensitivity, adhesion, and resolution) depending on whether or not the plasticizer is contained. Here, the sensitivity refers to a step 7 when an exposure machine (manufactured by Oak Co., Ltd.) HMW-201B having a high-pressure mercury lamp lamp is used to expose a stove 21-step tablet as a negative on a test piece. 0.0 level is 30 ° C./1 wt% aqueous sodium carbonate solution / exposure amount not removed by spray development for 60 seconds (mJ / cm ² ).
Adhesiveness and resolution are the values when exposed with the exposure amount having the above sensitivity, and a wiring pattern having a line width / space width of 10/400 to 50/400 (unit: μm) as an adhesive evaluation negative. For convenience, it is preferable to use a photo tool having a wiring pattern having a line width / space width of 10/10 to 50/50 (unit: μm) as a negative for resolution evaluation. In the case of sensitivity, the amount of change with or without a plasticizer is ± 20%, and in the case of adhesion, the amount of change with or without a plasticizer is ± In the case of resolution, the amount of change with and without a plasticizer is ± 20%.
The plasticizer used in the present invention has a melting point of 20 to 130 ° C, preferably 40 to 120 ° C, and more preferably 50 to 100 ° C. This temperature is equal to or lower than the temperature applied to the photosensitive element at the time of lamination, and the plasticizer is melted by the temperature applied at the time of lamination, thereby further improving the followability to unevenness. Moreover, it is effective for storage stability at the temperature below melting | fusing point which a plasticizer has in said range, and the edge fusion which resin oozes out from the edge part of the photosensitive element can be prevented.
As the plasticizer (D), for example, the general formula (II)

（式中、Ｒ^３からＲ^７は水素原子又は炭素数１〜３のアルキル基を示す）で表される化合物、これらの化合物のアルキル基に水酸基、エポキシ基、ハロゲン基等が置換した化合物などが挙げられる。
上記一般式（II）中のＲ^３からＲ^７で示される炭素数１〜３のアルキル基としては、例えば、メチル基、エチル基、プロピル基が挙げられる。これらは単独で又は２種以上を組み合わせて用いることができる。この他に、フタル酸系、リン酸系、脂肪酸系、エポキシ系、パラフィン系、分子量が１０００程度のオリゴマーなどが挙げられる。

(Wherein R ³ to R ⁷ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), compounds in which the alkyl group of these compounds is substituted with a hydroxyl group, an epoxy group, a halogen group, or the like Is mentioned.
Examples of the alkyl group having 1 to 3 carbon atoms represented by R ³ to R ⁷ in the general formula (II) include a methyl group, an ethyl group, and a propyl group. These can be used alone or in combination of two or more. In addition, phthalic acid-based, phosphoric acid-based, fatty acid-based, epoxy-based, paraffin-based, oligomers having a molecular weight of about 1000, and the like can be mentioned.

In the present invention described below, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, and (meth) acryloyl group means acryloyl group. And the corresponding methacryloyl group.
The (A) binder polymer used in the photosensitive resin composition of the present invention can be produced, for example, by radical polymerization of a polymerizable monomer.
(A) As the polymerizable monomer of the binder polymer, for example, a polymerizable styrene derivative substituted at the α-position or aromatic ring such as styrene, vinyl toluene, α-methylstyrene, or acrylamide such as diacetone acrylamide , Vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylamino (meth) acrylate Ethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (Meta) ak Luric acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate And maleic acid monoesters such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid.

  Examples of the (meth) acrylic acid alkyl ester include, for example, the general formula (I)

（式中、Ｒ^１は、水素原子又はメチル基を示し、Ｒ^２は炭素数１〜３のアルキル基を示す）で表される化合物、これらの化合物のアルキル基に水酸基、エポキシ基、ハロゲン基等が置換した化合物などが挙げられる。
上記一般式（Ｉ）中のＲ^２で示される炭素数１〜３のアルキル基としては、例えば、メチル基、エチル基、プロピル基が挙げられる。上記一般式（Ｉ）で表される単量体としては、例えば、（メタ）アクリル酸メチルエステル、（メタ）アクリル酸エチルエステル、（メタ）アクリル酸プロピルエステル等が挙げられる。これらは単独で又は２種以上を組み合わせて用いることができる。

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 3 carbon atoms), a hydroxyl group, an epoxy group, a halogen group in the alkyl group of these compounds And the like.
Examples of the alkyl group having 1 to 3 carbon atoms represented by R ² in the general formula (I) include a methyl group, an ethyl group, and a propyl group. Examples of the monomer represented by the general formula (I) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, and the like. These can be used alone or in combination of two or more.

In addition, the binder polymer as the component (A) in the present invention preferably contains a carboxyl group from the viewpoint of alkali developability. For example, a polymerizable monomer having a carboxyl group and other polymerizable monomers. Can be produced by radical polymerization. Moreover, it is preferable that the binder polymer which is (A) component in this invention contains styrene or a styrene derivative as a polymerizable monomer from a flexible viewpoint.
These binder polymers are used alone or in combination of two or more. Here, as the degree of dispersion when two or more kinds of binder polymers are combined, the degree of dispersion of the entire component (A) (polymer mixture) is used. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion are used. Examples thereof include a binder polymer. In this case, the dispersity (weight average molecular weight / number average molecular weight) is preferably 1.0 to 3.0, and more preferably 1.5 to 2.5. When the degree of dispersion exceeds 3.0, the adhesiveness and resolution tend to decrease. However, the weight average molecular weight and number average molecular weight in the present invention are values measured by gel permeation chromatography and converted to standard polystyrene.

The weight average molecular weight of the (A) binder polymer is preferably 20,000 to 300,000, and more preferably 40,000 to 150,000. When the weight average molecular weight is less than 20,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long.
(A) As a binder polymer, in addition to the polymer produced by radical polymerization of the above polymerizable monomer, the dispersity is preferably 1.0 to 3.0, for example, acrylic resin, styrene Resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin and the like. From the viewpoint of alkali developability, an acrylic resin is preferable. These can be used alone or in combination of two or more.
The acid value of the (A) binder polymer is preferably 100 to 500 mgKOH / g, and more preferably 100 to 300 mgKOH / g. When the acid value is less than 100 mgKOH / g, the development time tends to be delayed, and when it exceeds 500 mgKOH / g, the developer resistance of the photocured resist tends to be lowered.

  (B) As a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule, a bisphenol A (meth) acrylate compound and a polyhydric alcohol are reacted with α, β-unsaturated carboxylic acid. A compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, a urethane monomer such as a (meth) acrylate compound having a urethane bond, nonylphenyldioxylene (meth) acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β′- (Meth) acryloyloxyethyl-o-phthalate, (meth) acrylic acid al Examples thereof include kill esters and EO-modified nonylphenyl (meth) acrylate, but it is preferable to use a photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule. These may be used alone or in combination of two or more.

  Examples of the bisphenol A-based (meth) acrylate compound include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypoly). Propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Bisphenol A-based (meth) acrylate compounds and the like.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonane) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE- 00 (made by Shin-Nakamura Chemical Co., Ltd., product name) is commercially available, and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 (Shin-Nakamura Chemical Industry) It is commercially available as a product name). These may be used alone or in combination of two or more.

  Examples of the 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) a) Liloxynonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-((meta And acryloxyhexadecapropoxy) phenyl) propane. These may be used alone or in combination of two or more.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane. 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like. . These may be used alone or in combination of two or more.

Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. Polypropylene glycol di (meth) acrylate being 14, polyethylene polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraeth Xyltri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, polypropylene glycol di (meth) having 2 to 14 propylene groups ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Examples of the α, β-unsaturated carboxylic acid include (meth) acrylic acid.

  Examples of the glycidyl group-containing compound include trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4- (meth) acryloxy-2-hydroxy-propyloxy) phenyl, and the like.

Examples of the urethane monomer include a (meth) acryl monomer having an OH group at the β-position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction product, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups. Examples of the EO-modified urethane di (meth) acrylate include Shin-Nakamura Chemical Co., Ltd., product name UA-11, and the like. Examples of EO and PO-modified urethane di (meth) acrylate include Shin-Nakamura Chemical Co., Ltd., product name UA-13, and the like.
Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and the like. .

  Examples of the photopolymerization initiator of the component (C) in the present invention include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-. Diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] Aromatic ketones such as 2-morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenyl Anthraquinone, 2,3-diphenylanthraquinone 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, quinones such as 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl Benzoin ether compounds such as ether and benzoin phenyl ether, benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2 -(O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4 , 5-Diphenylimi Zole dimer, 2,4,5-triarylimidazole dimer such as 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9 , 9'-acridinyl) heptane, N-phenylglycine, N-phenylglycine derivatives, coumarin compounds and the like. Further, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may give the same and symmetric compounds, or differently give asymmetric compounds. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid. From the viewpoint of adhesion and sensitivity, 2,4,5-triarylimidazole dimer is more preferable. These are used alone or in combination of two or more.

The blending amount of the (A) binder polymer is preferably 30 to 80 parts by weight and more preferably 45 to 70 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). preferable. If the blending amount is less than 30 parts by weight, the photocured product tends to be brittle, and when used as a photosensitive element, the coating property tends to be inferior, and if it exceeds 80 parts by weight, the photosensitivity tends to be insufficient. is there.
The blending amount of the (B) photopolymerizable compound is preferably 20 to 60 parts by weight, and preferably 30 to 55 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). Is more preferable. If this amount is less than 20 parts by weight, the photosensitivity tends to be insufficient, and if it exceeds 60 parts by weight, the photocured product tends to be brittle.

The blending amount of the (C) photopolymerization initiator is preferably 0.1 to 20 parts by weight, and 0.2 to 5 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). More preferably, it is a part. If the blending amount is less than 0.1 parts by weight, the photosensitivity tends to be insufficient, and if it exceeds 20 parts by weight, the absorption on the surface of the composition increases during exposure and the internal photocuring is insufficient. Tend to be.
The blending amount of the (D) plasticizer is preferably 0.1 to 40 parts by weight, and 0.2 to 30 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). More preferably. If this amount is less than 0.1 parts by weight, the plasticizing effect tends to be insufficient, and if it exceeds 40 parts by weight, the photocured product tends to become brittle.

  In addition, the photosensitive resin composition of the present invention includes, if necessary, a dye such as malachite green, a photochromic agent such as tribromophenylsulfone or leuco crystal violet, a thermochromic inhibitor, a pigment, a filler, an antifoaming agent. Agent, flame retardant, stabilizer, adhesion-imparting agent, leveling agent, peeling accelerator, antioxidant, fragrance, imaging agent, thermal cross-linking agent, etc. with respect to 100 parts by weight of the total amount of component (A) and component (B) About 0.005 to 20 parts by weight. These are used alone or in combination of two or more.

If necessary, the photosensitive resin composition of the present invention may be a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. And can be applied as a solution having a solid content of about 30 to 60% by weight.
The photosensitive resin composition solution is not particularly limited, but a metal surface, for example, an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron, stainless steel, preferably copper, a copper-based alloy, an iron-based alloy. It is preferable that the surface is coated as a liquid resist and dried, and then coated with a protective film as necessary, or used in the form of a photosensitive element.
Moreover, although the thickness of the photosensitive resin composition layer changes with uses, it is preferable that it is 1-100 micrometers by the thickness after drying, and it is more preferable that it is 1-50 micrometers. If the thickness is less than 1 μm, it tends to be difficult to apply industrially.
The layer of the photosensitive resin composition preferably has a transmittance for ultraviolet rays having a wavelength of 365 nm of 5 to 75%, more preferably 7 to 60%, and particularly preferably 10 to 40%. . If the transmittance is less than 5%, the adhesion tends to be inferior, and if it exceeds 75%, the resolution tends to be inferior. The transmittance can be measured by a UV spectrometer, and examples of the UV spectrometer include a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

The photosensitive resin composition solution is applied onto a support and dried to form a layer of the photosensitive resin composition on the support, and a protective film is coated as necessary to form a photosensitive element.
When used as the photosensitive element, the support preferably has a thickness of 5 to 25 μm, more preferably 8 to 20 μm, and particularly preferably 10 to 16 μm. If the thickness is less than 5 μm, the support before development tends to be broken upon peeling, and if it exceeds 25 μm, the resolution tends to decrease. Examples of the support include polymer films having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester.
When used as the photosensitive element, the protective film preferably has a thickness of 5 to 30 μm, more preferably 10 to 28 μm, and particularly preferably 15 to 25 μm. When the thickness is less than 5 μm, the protective film tends to be broken during lamination, and when it exceeds 30 μm, the cost tends to be inferior.
In addition, since these support and protective film must be removable from the photosensitive resin composition layer later, they should not be subjected to a surface treatment that makes removal impossible. There is no limit and processing may be performed as necessary. Furthermore, these supports and protective films may be subjected to antistatic treatment as necessary.
The photosensitive element consisting of two layers of the support and the photosensitive resin composition layer thus obtained and the photosensitive element consisting of three layers of the support, the photosensitive resin composition layer and the protective film are, for example, The protective film is further laminated on the other surface of the photosensitive resin composition layer as it is, and is wound and stored in a roll shape.

When manufacturing the resist pattern using the photosensitive element, if the protective film is present, the protective film is removed, and then the photosensitive resin composition layer is heated and pressure-bonded to the circuit forming substrate. The method of laminating by doing, etc. are mentioned, It is preferable to laminate | stack under reduced pressure from the viewpoint of adhesiveness and followable | trackability. The surface to be laminated is usually a metal surface, but is not particularly limited. The heating temperature of the photosensitive resin composition layer is preferably 70 to 130 ° C. and the pressure bonding pressure is preferably about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). There are no particular restrictions on the conditions. If the photosensitive resin composition layer is heated to 70 to 130 ° C., it is not necessary to pre-heat the circuit forming substrate in advance, but the circuit forming substrate is pre-heated in order to further improve the stackability. You can also.
The photosensitive resin composition layer thus laminated is irradiated with actinic rays in an image form through a negative or positive mask pattern called an artwork. Under the present circumstances, when the polymer film which exists on the photosensitive resin composition layer is transparent, you may irradiate actinic light as it is, and when it is opaque, it is necessary to remove naturally. As the light source of actinic light, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp that emits ultraviolet rays effectively is used. Moreover, what emits visible light effectively, such as a photographic flood light bulb and a solar lamp, is also used.

  Next, after the exposure, when a support is present on the photosensitive resin composition layer, the support is removed, and then the unexposed area is removed and developed by wet development, dry development, etc. Manufacturing. In the case of wet development, development is performed by a known method such as spraying, rocking dipping, brushing, scraping, or the like, using a developer corresponding to the photosensitive resin composition such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. To do. As the developing solution, a safe and stable solution having good operability such as an alkaline aqueous solution is used. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate, potassium phosphate, and phosphoric acid. Alkali metal phosphates such as sodium and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used. Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5 wt% sodium carbonate, a dilute solution of 0.1 to 5 wt% potassium carbonate, a dilute solution of 0.1 to 5 wt% sodium hydroxide, A dilute solution of 0.1 to 5% by weight sodium tetraborate is preferred. Moreover, it is preferable to make pH of the alkaline aqueous solution used for image development into the range of 9-11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed. The aqueous developer comprises water or an alkaline aqueous solution and one or more organic solvents. Examples of the alkaline substance include borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2, morpholine, etc. are mentioned. The pH of the developer is preferably as low as possible within a range where the resist can be sufficiently developed, preferably pH 8-12, more preferably pH 9-10. Examples of the organic solvent include 3-acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. And monobutyl ether. These are used alone or in combination of two or more. The concentration of the organic solvent is usually preferably 2 to 90% by weight, and the temperature can be adjusted according to the developability. Further, a small amount of a surfactant, an antifoaming agent and the like can be mixed in the aqueous developer. Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. These organic solvents preferably add water in the range of 1 to 20% by weight in order to prevent ignition. Moreover, you may use together 2 or more types of image development methods as needed. Development methods include a dip method, a battle method, a spray method, brushing, and slapping, and the high pressure spray method is most suitable for improving the resolution.

As the treatment after development, the resist pattern may be further cured and used by performing heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 mJ / cm ² as necessary.
For etching the metal surface after development, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or a hydrogen peroxide-based etching solution can be used, but ferric chloride is used because of its good etch factor. It is desirable to use a solution.
When a printed wiring board is produced using the photosensitive element of the present invention, the surface of the circuit forming substrate is treated by a known method such as etching or plating using the developed resist pattern as a mask. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high throw solder plating, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating, nickel sulfamate plating, and hard There are gold plating such as gold plating and soft gold plating. Next, the resist pattern can be peeled off with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example. As this strongly alkaline aqueous solution, for example, a 1 to 10% by weight sodium hydroxide aqueous solution, a 1 to 10% by weight potassium hydroxide aqueous solution and the like are used. Examples of the peeling method include an immersion method and a spray method, and the immersion method and the spray method may be used alone or in combination. The printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board.

  Similar to the printed wiring board manufacturing method described above, the display board is laminated with a photosensitive element on a base material coated with a rib material, and after pattern exposure, the unexposed area is removed with a developer and subjected to sandblasting. After the pattern is formed, the cured portion of the resist material is manufactured by a method of peeling off from the substrate.

Hereinafter, the present invention will be described specifically by way of examples.
(Examples 1 to 4) and (Comparative Examples 1 to 4)
Using the plasticizer shown in Table 2, the materials shown in Table 1 were blended to obtain a photosensitive resin composition solution. Subsequently, the obtained photosensitive resin composition solution was uniformly applied onto a 16 μm-thick polyethylene terephthalate film (trade name G2-16, manufactured by Teijin Ltd.) and dried for 10 minutes with a 100 ° C. hot air convection dryer. Then, it was protected with a polyethylene protective film (trade name: NF-13, manufactured by Tamapoly Co., Ltd.) to obtain a photosensitive resin composition laminate. The film thickness after drying of the photosensitive resin composition layer was 40 μm.

（＊１）：２，２−ビス（４−（メタクリロキシペンタデカエトキシ）フェニル）プロパン、新中村化学工業株式会社製
（＊２）：γ-クロロ-β-ヒドロキシプロピル-β'-メタクリロイルオキシエチル-o-フタレート、日立化成工業株式会社製

(* 1): 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane, manufactured by Shin-Nakamura Chemical Co., Ltd. (* 2): γ-chloro-β-hydroxypropyl-β'-methacryloyloxy Ethyl-o-phthalate, manufactured by Hitachi Chemical Co., Ltd.

The following evaluation was performed about the photosensitive element of this invention.
(1) Follow-up property Using a commercially available photosensitive element on a copper-clad laminate with a 35 μm copper foil laminated in advance, a linear groove with a width of 100 μm and a depth of 5 to 20 μm is prepared by exposing, developing, etching and peeling. did. The grooved substrate was laminated by peeling the polyethylene film of the photosensitive element by the same method as described above. A negative film was used for this laminate, and the resulting resist image (line width / space width = 100 μm / 100 μm) was exposed so as to be perpendicular to the groove of the substrate, followed by development, etching, and peeling treatment. The groove depth at which the chipping / disconnection rate of the resist image (line shape) of the substrate was 10% was measured to determine the followability. The larger the value, the better the photosensitive layer is embedded in the deep groove, and the better the followability.

(2) Storage stability (edge fusion)
The photosensitive element 200m was wound on a roll and allowed to stand at 30 ° C. for 1 month to observe whether or not the photosensitive resin composition exuded from the roll end face.
The evaluation results are summarized in Table 3.

Examples 1-4 show the same photosensitivity, adhesiveness, and resolution as Comparative Example 1 in which no plasticizer is blended. As is apparent from Table 3, Examples 1-4 have good followability. And storage stability is also good. On the other hand, the comparative example 1 without addition of a plasticizer is inferior in followability. Moreover, Comparative Examples 2 and 3 of glycols blended as a plasticizer that does not correspond to the plasticizer of the present invention are inferior in followability, oozed out from the roll end face, and inferior in storage stability. Further, Comparative Example 4 using p-toluenesulfonic acid amide was inferior in followability and storage stability as in Comparative Examples 2 and 3.

Claims (9)

A photosensitive resin composition comprising a plasticizer having a melting point in the range of 20 to 130 ° C. A photosensitive resin composition comprising a plasticizer having a melting point lower than a laminating temperature. The photosensitive resin composition comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule, (C) a photopolymerization initiator, and (D) a plasticizer. The photosensitive resin composition of Claim 1 or Claim 2 formed by containing. Component (A), component (B), component (C) and component (D) of claim 3 are mixed in an amount of 100 parts by weight of component (A) and component (B). 30 to 80 parts by weight, 20 to 60 parts by weight of component (B), 0.1 to 20 parts by weight of component (C), and 0.1 to 40 parts by weight of component (D). The photosensitive resin composition as described in 2. The photosensitive element formed by apply | coating and drying the layer of the photosensitive resin composition in any one of Claim 1 thru | or 4 on a support body. 5. A protective film, wherein the layer of the photosensitive resin composition according to claim 1 is applied and dried on a support, and is further in contact with the layer of the photosensitive resin composition opposite to the support. A photosensitive element made by laminating layers. When there is a protective film, the photosensitive element according to claim 5 or 6 is peeled off so that the layer of the photosensitive resin composition is in close contact with the circuit forming substrate or the display forming substrate. A method for producing a resist pattern, comprising: laminating, irradiating an actinic ray in an image shape to photocuring an exposed portion, and removing an unexposed portion by development. A method for producing a printed wiring board, comprising etching or plating a circuit forming substrate on which a resist pattern is formed by the method for producing a resist pattern according to claim 7. A method for producing a display board, comprising a step of processing a display forming substrate on which a resist pattern is formed by sandblasting according to the method for producing a resist pattern according to claim 7.